Asymmetrical urea disazo dyestuffs



Patented May 8, i945 ASYMMETBICAL UREA DISAZO DYESTUFFS Otto Kaiser, Basel, Switzerland, assignor to the Swiss firm of Society of Chemical Industry Basle, Basel. Switzerland No Drawing. Application April zo, 1943, Serial No. 483,801. In Switzerland June 20,1942

in U. s. patent application Serial No. 434,009, filed March 9, 1942, (now Patent NO, 2,341,- 791) there are described new disaz ofdyestuffs of the general formula l cylic acid, R1 and R3 stand for aromatic nuclei of l the benzene series wherein the N=N-- and the groups stand in 1:4-position, to one another, R2 stands for an aromatic nucleus of the benzene series, in whichthe l and the n t. groups stand in another position than in the -1:2- position to one another, and R4 stands for anaromatic nucleus of the benzene series containing an OH group and ,a carboxyl group in ortho-position to this OH group.

These dyestufis which are monosulfonic acids of definite asynunetrical urea-likedisazo-dya stuffs, represent valuable direct dyeing dyestuffs which are characterizedbythe strength of the ,TClaims. (01. 260-175) nucleus stand in 1:4-posit'ion to one another, -N=N-- and l .1

.N v groups attached to one and the same benzene nucleus standalso in 1:4-p'osition to one another,

the

0 ll l '-C groups and --N=N or 1H r ,N+ groups .attached to one and the same benzene nucleusstand however inanother positionthan in 1:2- position to one another, and B is always linked directly to a nitrogen atom of the connecting member 117, and wherein finally that benzene nucleus which is linlred directly to the ll. r ogroup is free from .sulfonic groups andR is also free from'sulfonic groups if the CO- group is linkeddirectly to the radicalRz. r

The new dyestuffs are obtained by the methods usual for such products. In accordance with th dyeings produced with their aid and by the very good wet fastness properties of these dyeings after-treated with agents yielding copper.

It has beenfound that not only the urea-like, disazo-dyestuffs possess these valuable properties, but that they are inherentquite generally in the monosulfonic acids of the asymmetrical ureas of the general formula 1 l l l l R-IR1- t-RgN I TRaN-=NR4 wherein It and R4 stand for aromatic nuclei of theben z ene series containing an OH- group and a carboxyl group in ortho-position to this OH- group, one of the two :rs stands for a --N=N- group and the other for a II I Q N group, R1, R2 and R3 stand for aromatic nuclei of the benzene series, wherein any groups attached to one and the same benzene foregoing data, the components forthe various methods which are described further below should be, so selected'that the final dyestufi contains only lonesulfonic group, those benezene nuclei which arejlinkeddirectly to the C0- grou-p carrying no sulfom'c groups and R being also free from sulfonic groups if the CO group is linked directly to, the'radical R2.

The new dyestuffs can be, made for example by combining 1 mol of an azo-dyestufi of the general formula j Rl ',R1-J: R2 NH2 in which R, 3:, R1 and Rz have the meanings above given. with 1 mol of an 1 azo-dyestufi of the general formula R4N= NR3 NH2 V in which R; and R3 have the aforesaid meanings by treatment with phosgene to produce the corresponding urea derivative.

Another method consists in diazotizing 1 mol of an aminoazo-dyestufi of the general iormula stuffs consists in tetrazotizing asymmetrical ureas of the general formula NHPK 1IB1ITI%ITIBQNHQ wherein K, B1 and B2 stand for aromatic nuclei .of the benzene series and y stands for a.

.0.-.1\1 II I 0 H group,

and -NHzugroups standingiin her-position to one another and and V.

Or.-NH2 groups standing in another position thanin 1 :2-position to one another, and coupling them-with2 mols of the same ordifferent orthohydroxycarboxylic acids of the benzene series.

Productscorresponding tothe above explained generalforr'nula are for example compounds such as 4-hydroxy- 1:1 azobenzene 4-(4-am ino-2"-sulfo) -carboylamino benzene-3-carboxylic acid, 4 (3" amino) benzoylamino .-"1;1"- azobenzenei-hy droxy-Z-sulfo-5carboxylic acid, and the like.

To this class belong also products such as 4 hydrOXY-II1-azobenzene3'-(i" amino) carboylaminobenzene-3 carboxylic acid, i-hydroxy- E-methyl 1:1f azobenzene-3'-(4"-amino) -carboylaminobenzene 3 carboxylic acid, 4 hydroxy-2-methyl-1 1 '-azoben zene-3' (4' -amino) carboylaminobenzene-3-carboxylic acid, 4-hydroxy-l':1'azobenzene-3'-(4"-amino-3"-sulfo) carboylaminob enzene-3-carboxylic acid, 4hy droxy-l:1-azobenzene.-4-(4" amino) carboylaminobenzene-3-carboxylic acid, 4-hydroxy-5- methyl 1:1 azobenzene 4 (i amino -3-. sulfo)-carboylaminobenzene-3-carboxylic acid, 4-amino-1:1-azobenzene4-(4" hydroxy 3"- carboxy) carboylaminobenzene, 4 amino 2 methyl 1:1 azobenzene 4'-(4"-hydroxy-3" carboxy) carboylaminobenzene, 4 amino 2 methyl-5-methoxy-l:1'-azobenzene-4'-(4" hydroxy 3" carboxy) carboylaminobenzene, 4- amino 2 meth-yl -111"-azobenzene-4,-(4"-hydrox-y 3 carboxy.-5"-methyl) .-carboylamin0- benzene, 4- amino 2:-methyl-.1:l'razobenzenes 4 (4"-hydroxy-3"-carboxy 6" methyl) .car-

. HO-QN: oo'u boylaminobenzene, 4-amino-2-methy1-1: 1- ambenzene-3 (4" -hydroxy-3"-carboxy) -carboylaminobenzene, 4 amino 2 methyl-fi-methoxy- 1:1-azobenzene-3'-(4-hydroxy-3" carboxy)- carboylaminobenzene, 4 amino-2-methyl-1:1'- azobenzene 4' (4 hydroxy- 3"-carboxy-5"- sulfo) -carboylaminobenzene, 4-amino-2-methyl- 1:1 azobenzene, 4F(4"-hydroxy-3"-carboxy- 6" sulfo) carboylaminobenzene, 4 amino-2- methyl 1:1 azobenzene 4-(2"-hydroxy-3"- carboxy 5" Asuifo) carboylaminobenzene, 4- amino-2emethyl-5-methoxy- 1:1 -azobenzene -3 ('2" hydroxy 3" carboxy 5"-sulfo) -carboylaminobenzene and the like.

Products, which may correspond for example to the above explained general formula are for example 4'-amino-1:1-az0benzene-4-hydroxy-B-carboxylic acid, 4'-amino-2'-methyl- 1: 1 -azobenzene-A-hydroxy-3ecarboxylic acid, if-.amino -W- methoxy 2'-methyl 1 21.- azobenzenesfl hydroxy-3-carboxy1ic acid, 4'-.amino.-3"- methoxyl-hydroxy 1: 1'- azobenzeneeifiecarboxe.

ylic acid, 4'-amino-3' -methy1,-4-hydroxy-1:1'-

aZobenzene-3-carboxylic acid and the like.

Asasymmetrical ureas of'the above explained general formula, l

there may be cfurther used: products such as 4-amino-4' (4' -amino -benzoylamino-diphenylsulfo).ebenzoylaminoediphenylurea, 4-amino-3 (4 '-amino) -carboylaminobenzeneediphenylurea, 4-amino 4-(4-amino)'- carboylaminobenzenediphenylurea, 4-amino.-3'- (4-'-amino) -carboyl aminobenzene diphenylurea 3 sulfonic 4-amino-3- (4"- amino-3"-sulfo) -carboylaminodiphenylurea, 4-amino-4- (4' '-amino-3-sulfo) carboylamino-diphenylurea, and the like.

The'following examples illustrate the invene tion,,but arenotto be regarded as limiting'it in anyway, the parts being by weight:

Example 1 reduced at -70" C. with 42 parts of crystallized sodium sulfide dissolved in '75 parts of water, to the aminobenzoyl product.

45.6 parts of the precipitated reduction product are dissolved in 3000 parts oi water with 25.7 parts of 4-amino-e-hydr oxy-1:leazobenzena 3'-carboxylic acid with addition of, sodium. car.-

bonate until the reaction is distinctly alkaline,

and the whole is treated with phosgene for 20 hours at 30-40 (2., while stirring, until, a 'free NHzgroup can no longer be detected. The

formed urea derivative is precipitated as sodium salt, filtered and dried. The new dyestuff which corresponds to the formula coon represents a yellow brown powder and dyes cotton in a feebly alkalinebath mixed with a copper salt solution from copper sulfate and sodium tartrate, greenish yellow tints which are fast to washing.

The dyestuffs obtained by replacing the 1- hydroxybenzene-Z-carboxylic acid mentioned in the first paragraph of this example by the 1-hydroxy-6- or --methylbenzene-Z-carboxylic Ho i H 0 CODE ([JH: Q QWGr H 0 i B: 00011 SOaH Example 2 37.6 parts of 4'-(4"-amino)- benzoylamino- 1:1 '-azobenzene-4-hydroxy-3-carboxylic. acid are dissolved in 3000 parts of water with 33.7 parts of 4'-ar'nino-1i1-azobenzene 4-hydroxy-3-carboxy-2'-sulfonic acid with addition of sodium carbonate until the reaction is distinctly alkaline,

and the whole is treated with phosgene for hours at -40 C., while .stirring, until a free NH2- group can no longer be detected. The formed urea derivative is precipitatedas sodium salt, filtered and dried. It corresponds to the formula a f H O COOH dissolved in 3000 parts of water with 38.1 parts of 4'- amino 1:1'- azobenzene 2 '-.methyl-5i'- methoxy-4-hydroxy-3-carboxy -.5 sulfonic acid with addition of sodium carbonate until the reaction is distinctly alkaline, and the whole is treated with phosgene for 20 hours at 30-40" C., while stirring, until a free NH2 group can no longer be detected. The formed urea derivative is precipitatedas sodium salt, filtered and acid, or by replacing the 3-nitrobenzoylchloride l0 dried, It corresponds to the formula represents an orange powder and dyes cotton in a feebly alkaline bath mixed with a copper salt solution from copper sulfate and sodium tartrate, reddish yellow tints which are fast to washing.

Similar dyestuffs are formed when replacing the 4-(4"-amino) -benzoylamino 1:1- azobencoon zene-4-hydroxy-3-carboxylic acid by the 4- (4"- amino) benzoylamino 1:1'- azobenzene 4 -hydroxy-5-methyl-3-carboxylic acid, or i the 4'- amino-l :1-azobenzene-2'-methyl-5'-methoxy-4- hydroxy-ti-carboxy-5-sulfonic acid by the 4- amino-1:1"-azobenzene 2'- methyl-5-methoxy- 2-hydroxy-3-carboxy-5-sulfonic acid. Such a product corresponds for example to the formula com on CODE 6 i*t*iQ C o H 0 H CH5 7 S033 Example 4 47.1 parts of theaminoazo-dyestufi obtained by saponifying the acetyl group of the monoazodyestuff from diazotized l.-(4-aminobenzoy1)- amino-4-acetylaminobenzene-2-sulfonic acid and N=N OH S0311 GOOH represents a yellow powder and dyes cotton 2-hydroxybenzene-l-carboxylic acid are dissolved a feebly alkaline bath mixed with .a copper salt solution from copper sulfate and sodium tartrate,

greenish yellow tints. which are fast to washing.

Here, too, the l"-(4"-amino) -benz"oylamino- 1:1'-azobenzene-4-hydroxy 3-carboxylic acid or the 4-amino-1 l-azobenzene-4-hydroxy-3-carin 3000 parts of water with 25.7 parts of -amino boxy-2'-sulfonic acid can be replaced by such compounds in the manufacture of which l-hydroxy-5-methyl benzene 2 carboxylic acid or Example 3 37.6 parts of 4-(4" -amino)-benzoylamino- 1':1'-azobenzene-4-hydroxy-3-carboxylic acid are represents a yellow brownpowder and dyes cotwith addition of sodium carbonate until the reaction is distinctly alkaline, and the Whole is treated with phcsgene for 20 houre at 30-40 C., while stirring, until a free NH2 group can no longer be detected. The formed urea derivative is precipitated as sodium salt, filtered and dried. It corresponds to the formula COOH ton in a feebly alkaline bath mixed with a copper salt solution from copper sulfate and sodium tartrate, yellow tints which are fast to washing.

. Here, too, the starting products canbe replaced by such products in the manufacture of which 1-hydroxy-5-methyl- 01' l-hydroxy-S-methylben- 1-liydrdxybenzene 2=carboxylic acid.

Example v 27.2 parts of 4-(4'-aminobenzoyl)amino1- hydroxybenzene-2-carboxylic acid are diazotized in usual manner in 200 parts of water at 5 C. with 6;!) partsof sodium nitrite and parts of concentrated hydrochloric acid; andthe diazonium salt thus obtained is coupled with 10.7 parts of l -aminor-S-methylbenzene dissolved in 10 parts parts of concentrated hydrochloric acid and 200 parts of water. The formed monoazo dyestufi is heated to 80 C. and separated as sodium salt..

39 par'ts'of the separated product are dissolved in 3000 parts of water with 38.1 parts of 4'- amino 1 :1 azobenzene 2'-methyl5'methoxy- 4-hydroxy-3 carboxy-5-sulfonic acid with additionof sodium carbonate until the reactionis dis- .tinctly alkaline, and the whole is treated with phosgene for hours at ISO-40 C., while stirring,- until a free NHZ- group can no longer be detected. The urea derivative is precipitated as sodium salt, filtered and dried. It corresponds to the formula I H O H CH3 coon the l-aminobenzene is used, it should be applied in the form of its w-methanesulfonic acid and the w-methanesulfonic acid is split oif in known inanner after coupling is complete. Moreover, the 4- amino-1:1'-azoloenzene-2-methyl-5 -meth0Xyi-4- hydroxy-3-carboXy-5-su1fonic acid can be replaced bythe 4-amin0-1 :1'-azoldenzene-2'-methyl-5-methoxy-2-hydroxy-S-carlooxy 5 sulfonic 35 with 13.8 parts of 2 -hydroxybenzoic aciddissolved yl-4;-hydroxy-S-carboxy-B-sulfonic acid, the 4;- amino 1:1 -azobenzene 2 :5 dimethyl-4-hydroxy-3-carboXy-5-sulfonic acid or the 4-ami'no-" 1 l-azobenZene"4-hydroXy-3-carboXy-5-sulfonic acid, dyestuffs which behave similarly being thus also obtained Finally, the 4-(4'-aminobenzoyl) COQH amino-1-hydroxybenzene-2-carboxylic acid can be replacdby the 4-(3'-aminobenzoyl)-ainino- 1 hydroxybenzene-2-carboxy1ic acid, Such a dyestufi corresponds for example to the formula coon OCH;

. Example 6 droxybenzene-3mar oxylic acid are dia'zotizd in usual manner at 5 C. with"6.9 parts of sodium nitrite and 25 parts of concentrated hydrochloric acid, and the diazonium salt thus obtained is coupled with 10.7 parts of 1-amino-3-n' ethylbenzene dissolved in 10 parts of concentrated hydro chloric acid and 200 parts of water. The armed;

monoazo=dyestuff is heated to C. and separated as sodium salt.

39 parts of the separated product are dissolved in 3000 partsof water with 18.8 parts of 1:4-diaminobenZene-Z-sulfonic acid with addition of sodium carbonate until the reaction is distinctly alkaline, and the whole is' treated with phosgene for 20 hours at 304m c, while stirring, until only one free NH2- group can be detected. The

OCHi 0003' in 200 parts of Water with 4 parts of sodiumhydroxide and 30 parts of sodium carbonate. The

dyestuff which has beenformed is precipitated as sodium salt, filtered and dried. It corresponds to the formula COOH H O H O H CH3 t represents a brown powder and dyes cotton in afeebly alkaline bath mixed with a copper saltfrom the 1-(4'-aminobenzoyl). amin0 4 hydroxybenzene-3-carboxylic acid-S-sulfonic acid, and replacing the operations described in the 2nd paragraph of this example by a linkage with the 4 amino 4'- hydroxy -l;1'-azobenZene3'-car boxylic acid by means of phosgena'there is obtained aproduct'of the formula 1 H o H CH3 COOH which dyes cotton yellow tints, the wet fastness properties of which are improved by treatment with agents yielding copper.

When starting for instance in the first paragraph of this example.

Example 7 istreated with phosgene-for 20 hours at 30-40 0.,

while stirrin l ntil only one free NH2- group can be detected. The-formed urea is separated, dissolved as sodium salt at. 60 C. in 2000 parts of water, and 18.5 parts of -nitrobenzoylchloride mixed with 5 parts of acetone are added, while stirring. The formed nitrobenzoyl product is reduced at boiling temperature in 1000 parts of water, 200 parts of. iron filings and 20 parts of acetic acid, to the aminobenzoylproduct. The.

latter is then saponified to the diamine in1000 parts of water with 30 parts of sodium hydroxide by heating it for minutes at 90 C., and isolated by acidifying.

41.3 parts of the 'reduced and saponified product are dissolved neutral in 200 parts of water by addition of. sodium hydroxide, and diazotized with 13.8 parts of sodium nitrite and 50 parts of concentrated hydrochloric acid at 5-:10 C. The precipitated diazonium salt is coupled at 0 C. with 27.6 partsof 2-hydroxybenzoic acid dissolved with 8 parts of sodium hydroxide and 60 parts of sodiumcarbonate in 300 parts of water. The formed dyestuff is precipitatedas sodium salt, filtered and dried. It corresponds to theformula 3 l y l l I H. H L

coon

represents a dark brown powder and dyes cotton in a feebly alkaline bath mixed with a copper salt solution from copper sulfate andsodium tartratem 100 parts of cotton are introduced at 40-50? C. into a dye-bath containing 3000 parts of water, 0.6 part of the dyestuif prepared according to Example 1, 1st paragraph, and 2 parts of anhydrous sodium carbonate. 9095 C. within /2 hour, 30 parts, of crystallized sodium sulfate are added and dyeing is continued for. hour at this temperature. A solution of 2 parts of crystallized copper sulfate and 2.5 parts of tartaric acid in 100 parts of water, which has been neutralized with caustic soda solution, is added to the dye-bath and the cotton is treated for hour at about 95 C. The cotton is rinsed as usual and dried. It is dyed fast greenish yellow tints.

The dyestuifs of the present invention can be used also for dyeing mixed fabrics, for example mixtures of wool and viscose cellulose wool. In such cases it is advantageous to dye in a neutral bath in the presence of sodium or potassium chromate.

What I claim is:

1. The mono-sulfonic acids of the asymmetrical urea-like disazo-dyestufls of the general formula i H R-a:R -1R2NGNR3-N=NR4 wherein R and R4 each standsfor an aromatic nucleus of the benzene series containing an OH group and a carboxyl group in ortho-position to of 60 parts of sodium carbonate, and the solution 1 The bathisheated to this OH group, one of the two :rs stands for a -N=N--group and the other for a l 1 o n I! l C-N I group, R1, R2 and R3 each stands for an aromatic nucleus of the benzene series, wherein any Iii, N

groups attached to one and the same benzene nucleus stand in 1:4-position to one another, -N=N and groups attached to one and the same benzene nucleus stand also in lz i-position to one an other, the

and

i an groups attached to one and the same benzene nucleus stand in another position than in 1:2- position to one another, the

I r y and --N=N groups attached to one and the same benzene nucleus stand in another position than in.1:2-positionto one another, and R is always linked directly to a nitrogen atom of the connecting member an, and wherein finally that benzene nucleus whichis linked directly to the group is free from sulfonic groups and R is also free from sulfonic groups if the CO group is linked directly tothe radical R2, which dyestuffs are yellow to brown powders dyeing the vegetable fiber yellow tints, the wet fastness properties of which are improved by after treatment with agents yielding copper.

2. The mono-sulfonic acids ofthe asymmetrical urea-like disazo-dyestuffs of the general formula wherein R and R4 each stands for an aromatic nucleus of the benzene series containing an OH group and a carboxyl group in ortho-position to this OH group, R1 stands for an aromatic nucleus of the benzene series wherein the ll group and the N=N-- group stand in another position than in ortho-position to one another, and R2 and R3 each stands for an aromatic nucleus of the benzene series, the N=N group and the l group standing in lie-position to one another,

and wherein neither the radical R1 nor the; radimetrical urea-like disazo dyestuffs of the general cal R2 contains the sulfonic' group, which dyeformula stufis are yellow to brown powders dyeing the I? l I? vegetable fiber yellow tints, the wet fastness 4 1 properties of which are improved by after-treat- 5 'N f F I ment with agents yielding copper. wherein R and R4 achstandsfor an aromatic 3. The mo'nosulfonic acids of the asymnucleus of the' benzene series containing an 0115-.

metrical urea-like disazo-dyestuffs of the general group and a carboxyl group orthd-position to formula v H l0 nucleus of the benzene series in which the s r H o H and the -N=N-' groups stand in another pos'i each Stands. M an [5 tion than in ortho' p'o's ition to one another, R; and aromatic nucleus of the benzene series, -the I R5 each stands for an aromatic nucleus of the gmup 5nd the j benzene series, the --N: N group and the Y H 0 l I g, g ii it a 20 group standing in lz4-position to one another;

r up standing in :f p sition t on a t er, and, the sulfonic group linked. to one of the R1 and R4 each containing an OH- group and a radicals R1; R2 and R4, which dyestuffs are yellow carboxyl group in ortho-position to this OH to brown powders dyeing the vegetable fib'er yelgroup and R4 containing the sulfomc group, low tints, the wetfastness properties of which wh ch dyestu fisareyellowto brownpowders dye- 25 are improved by after-treatment with agents ing the vegetablefiber yellow tints; the Wet fastyielding copper. V ness properties of which are improved by after- 6. The dyestuff corresponding in the free form treatment with agents yielding copper. to the formula CHa U Ho fNQNQN-C -N-CNON 6h OOH SOaH 4. The dyestuff corresponding in its fi form to the formula 5. The mono-sulfonic acids of the asymto the formula 'Z The dyestufi corresponding in the free form GTTC this OH group,; R2 stands for an aromatic- 

